DE1911227C - Process for the production of organosilicon sulfides - Google Patents

Description

In organosilicon chemistry it is known that Compounds with halogen atoms in the ^ position to the Si atom are ·: are relatively unstable. Out For this reason, substitution reactions in the presence of certain solvents, for example alcoholic alkali to be carried out, practically impossible, since this very quickly splits the Si-C bonding takes place. For example, is general known that / 9-chloroethyltriethylsilane is significantly less stable against A icali metal power than the corresponding JO (x-isomers; by aqueous or alcoholic alkali metal solutions there is a rapid and quantitative formation of ethylene, with liberation of the chloride ion triggered and even by sodium acetate in glacial acetic acid or water alone become the similarly built compounds of the formulas

The inventive method of manufacture of organosilicon sulfides of the general formula

Ri Ri

R ₁₁ Si-CCSR "

wherein R is a monovalent hydrocarbon radical without aliphatic multiple bonds, an alkoxy, acyloxy-aryloxy or thiohydrocarbon radical, R 'Un hydrogen atom or monovalent hydrocarbon radical without aliphatic multiple bonds and R "is a hydrogen atom, a monovalent hydrocarbon radical without aliphatic multiple bonds, or a remainder of the formulas

O S

Y_C

O — C—

CH ₃ CH ₂ (Cl) ₈ SiCHaCH ₈ Cl
CH ₃ CH ₃ Si (F) ₂ CH ₂ CH ₈ Cl

decomposed.

In contrast, the present invention relates to a process for the preparation of organosilicon sulfides through a substitution reaction using of silicon compounds which contain a halogen atom in the / 3-position to the Si atom. The procedure can be carried out in the presence or absence of inert organic solvents. in the In view of the prior art, it is unexpected and surprising that here, in contrast to the expected split a substitution takes place.

The organosilicon sulfides obtainable by the process according to the invention are valuable adhesion promoters and intermediates for compounds which can be used as water repellants or antioxidants.

The process according to the invention therefore makes organosilicon sulfides simpler and more economical Way more accessible than with the previously known methods.

S O S

Ii ii ii

Y_S - C— Y ₈ -NC- or Y ₈ -NC-

mean, where Y is a monovalent hydrocarbon radical with 1 to 6 carbon atoms without aliphatic multiple bonds is characterized in that compounds of the general formula

R, Si - C - C - X

(A)

CH ₃

(CH ₃ O) ₂ Si - CH ₂ CH ₈ CI

CH ₁ CHoCH ₂ CH ₂ SNa

CH ₃ CH ₈ CH ₈ CH ₈ SH in which R and R 'have the meaning given and X is a chlorine, bromine or iodine atom, with compounds of the general formula

R "SM (B)

where R "has the meaning given and M is an alkali or alkaline earth equivalent will.

The 'inventive method is exothermic; it can be illustrated by the following reaction scheme will:

CH ₃
► (CH ₃ O) ₈ Si - CH ₈ CH ₂ S - CH ₂ CH ₂ CH ₂ CH ₃ ;

the temperature therefore does not play a decisive role. It is advantageous if the temperature is kept above room temperature in order to increase the rate of the reaction. In addition, it is advantageous if the temperature ^{does not exceed 150 °} C., since temperatures above 150 ^° C. can trigger disruptive side reactions, which is expressed in reduced yields.

The reaction can be carried out in the absence or in the presence of an inert organic solvent will. However, it is advantageous to use a solvent to ensure that the Alkali or alkaline earth metal thiolate is at least partially present in dissolved form.

It is also advantageous if the inventive Process carried out in a practically inert atmosphere or in a closed system is to exclude the action of oxygen, which intervene in the reaction and become undesirable Can lead to side reactions.

When carrying out the process according to the invention, the addition of the alkali metal to an excess of mercaptan or to an inert organic solvent has proven useful. As already mentioned, the primary purpose of the solvent is to guarantee that the compound (B) is at least partially dissolved. Excess mercaptan or an inert organic solvent which contains mercaptan is therefore preferred, since a thick slurry is formed in the absence of excess mercaptan or a solvent containing it. It follows that the reactant containing the halogen atom on the Si atom / 3-position is preferably slowly added in small amounts; then the salt formed is filtered off and the desired organic silicon sulfide is obtained by distillation. . , "
example 1

5 g of sodium metal were introduced into K) O g of butanethiol. Then 16.8 g of 2-chloroethyl were slowly

methyldimcthoxysilane added in small amounts. When the reaction had ended, the salt was filtered off. 14.3 g (64.3 "of theory) of the compound were obtained the formula

(CH ₃ O) ₈ Si - CH ₂ CH ₈ - S - CH ₈ CH ₈ CH ₁ CH ₉ -CH ₃

receive. This connection was confirmed by the data of elemental analysis.

Example 2

24.0 g butanethiol and 1.15 g metallic sodium »5 were reacted under nitrogen. The resulting solution of the thiolate of the formula

CH ₃ CH ₈ CH ₈ CH ₈ SNa

20th

and butyl mercaptan was heated to 80 ⁰ C and then slowly added dropwise within one hour with 12.2 g of 2-bromopropyltrimethoxysilane. The temperature (80 ^° C.) was maintained for 20 hours. The salts were then centrifuged, separated off and washed with hexane. 2.8 g (22% of theory) of the compound of the formula Nuclear Magnetic Resonance Spectrum:

group Protons T values Protons
calculated SlCH ₃
Himself, ,
C-CH ₃ ....
(C-CH,), ..
(S-CH,), ..
(OCH ₃ ), 2.9
I ^{5> 1}
4.2
3.9
5.9 9.93
9.1
9.5
9.5
6.55 3.0
5.0
4.0
4.0
6.0

Example 2 CH ₃

(CHsO) ₃ SiCH ₈ CHSC ₄ H,

Degree of purity: 99 ° / ₀ ; n% = 1.4461 (determined by gas-liquid chromatography).

Nuclear magnetic resonance spectrum:

SCH ₈ CH ₈ CH ₂ CH ₃
(CH ₃ O) ₃ Si - CH ₈ CHCH ₃

30th

receive. The structure of this compound was determined by mass spectrum analysis, nuclear magnetic resonance measurement and infrared spectrum confirmed.

Example 3

1.82 g of propanethiol were weighed into a 9 mm diameter glass tube which was cooled with ice. Then 15 ml (1.6 mol) of butyllithium in hexane were added to the glass tube and finally 4.04 g of 2-chloroethylmethyldimethoxysilane and hexane (25 ml) were added. The glass tube was then melted shut and ^{heated to 100 °} C. for 16 hours. Then the salts were removed by filtration. There were 2.18 g (47.7 ° / ₀ of theory) of the compound of formula

CH ₃
(CH ₃ O) ₈ Si-CH ₈ CH ₈ SCH ₈ CH ₈ CH ₃

group Protons 1 3.0 Protons
calculated i mass: 252 M. T values 9.08 CH ₈ -CH ₃ I 12.0 9.0 .C ₁₀ SiO ₃ H 252.45 CH ₈ -CH ₃ * 8.72 SiCH ₈ I. Mass spectrography: 12.0 theoretical mass: CH - CH ₃ * CHCH ₃ .... displayed SCH ₈ contains Si 7.55 SCH 3.0 SiCH ₈ 6.05 SiOCH ₃ .... 9.0

Example 3 (CH ₃ O) ₈ CH ₃ SiCH ₈ CH ₈ SCH ₈ CH ₈ CH ₃

n'ä = 1.4515; Bp: 120 ° C / 20 mm Hg; IR spectrum shows bands for SiOCH ₃ , SiCH ₃ and CH ₂ S.

Nuclear magnetic resonance spectrum:

receive. The structure of this compound was determined by mass spectrum analysis, nuclear magnetic resonance measurement and infrared spectrum confirmed.

Physical data
to supplement the examples

example 1
CH ₃

(CH ₃ O) ₃ SiCH ₈ CH ₈ SC ₁ H ₉

Bp: 100 ° C / 10mm Hg; n'f - 1.4528; J ₈₅ = 0.9528; Rd = 0.2836 (Rd calculated: 0.2832).

55

60

group Protons 2.3 Protons
calculated T values SiCH ₃ .... 3.1 3.9 3.0 9.92 SiCH ₈ .... 1 4.8 5.9 5.0 8.85 to 9.3 C-CH ₃ .. J C-CH ₂ .. 2.0 8.2 to 8.3 SCH ₂ 4.0 7.3 to 7.7 SiOCH ₃ .. 6.0 6.53

Claims (1)

Claim: Process for the production of organosilicon sulfides the general formula R, Ro ! i R _n Si-CCSR " where R is a monovalent hydrocarbon residue without aliphatic multiple bonds, an alkoxy, acyloxy, aryloxy or thio-hydrocarbon radical, R 'is a hydrogen atom or a monovalent hydrocarbon radical without an aliphatic Multiple bonds and R "is a hydrogen atom, a monovalent hydrocarbon off remainder without aliphatic multiple bonds, or a remainder of the Formulas NsC- Y — C— Y —O - C- or Y — S — C— Y, —N — C— Y ₁ -NC- mean, where Y is a monovalent hydrocarbon radical with 1 to 6 carbon atoms without aliphatic Multiple bonds is characterized in that compounds of the general formula Ra Ra ! I (A) R ₈ Si-CCX where R and R 'have the meaning given and X is a chlorine, bromine or iodine atom, with compounds dtr general formula R "SM (B) where R "has the meaning given and M is an alkali or alkaline earth equivalent, iimge be fetted.